Thermoplastic polymer compositions plasticized with certain esters of substituted 1, 5-pentanediols



United States Patent THERMOPLASTIC POLYMER COMPOSITIONS PLASTICIZED WITH CERTAIN ESTERS OF SUBSTITUTED 1,5-PENTANEDIOLS Curtis W. Smith, Berkeley, Calif., assignor to Shell Development Company, New York, N. Y., a corporation of Delaware No Drawing. Application April 30, 1954, Serial No. 426,926

11 Claims. (Cl. 260--31.4)

This invention relates to the plasticization of resinous compositions. More particularly, the invention relates to thermoplastic polymer compositions plasticized with a special group of polyol esters.

Specifically, the invention provides new and particularly useful compositions comprising a thermoplastic polymer, and particularly a thermoplastic vinyl halide polymer, having incorporated therein a plasticizer comprising an ester of (1) a substituted 1,5-pentanediol wherein a chain carbon atom immediately adjacent to one of the terminal hydroxyl-bearing carbon atoms is a tertiary carbon atom, and a chain carbon atom adjacent to the other hydroxylbearing carbon atom is a quaternary carbon atom, one of the carbon atoms to which the said quaternary carbon atom is attached being the carbon atom of an ethersubstituted alkyl group, such as, for example, 2,4-dimethyl-Z-methoxymethyl-1,5-pentanediol, and (2) carboxylic acids and/ or carboxylic acid esters and preferably those acids and acid esters containing at least 6 carbon atoms.

This application is a continuation-in-part of my application Serial No. 253,763, filed October 29, 1951, now U. S. Patent 2,691,663.

Thermoplastic polymers, and especially the thermoplastic vinyl halide polymers, are generally quite brittle and are difiicult to mill and mold. To overcome these difii-,

culties, it is common practice to mix the polymer with a plasticizing material, such as di(2-ethylhexyl) phthalate, dibutyl sebacate and tricresyl phosphate. Compositions containing these plasticizing materials can be readily worked on roll mills and easily molded or extruded to form flexible sheets or solid articles. Finely divided vinyl polymers may also be mixed with large quantities of liquid plasticizers to form plastisol or organosol compositions that can be spread as a paste on cloth or metal panels and cured to form flexible coatings or films.

It has been found, however, that the compounds suggested heretofore as plasticizers are not entirely satisfactory for many applications. Many of the suggested plasticizers, for example, are readily lost from the composition through migration and/ or volatilization and the composition again becomes brittle and easily cracked. This is particularly true of the conventional monomeric estertype plasticizers.

It has also been found that the addition of the suggested plasticizers has a deleterious effect on many of the other important properties of the finished composition. The addition of the plasticizers in amounts sufiicient to bring about the desired flexibility, for example, generally decreases the tensile strength of the product and makes them soft and supple. Such products are unable to be used for many applications, such as in the preparation of floor tile and coatings for seat covers, etc., where the finished product must also be hard and tough as well as being flexible. The addition of the plasticizers also in many cases seriously effects the odor and color as well as the water and alkali resistance of the finished composition. These defects make the compositions un- 'ice suited for use in the preparation of many household and clothing articles, such as table covers, boots, etc.

Various unsuccessful attempts have been made in the past to correct these difiiculties. It was felt that the use of high molecular weight materials as plasticizers would prevent the subsequent loss through migration and/or volatilization, but it has been found that many of these materials are still subject to migration and evaporation, and in addition, they are generally incompatible at the desired loadings with the thermoplastic polymers, fail to impart the desired processability and flexibility, and still seriously effect the odor, color and Water resistance of the resulting composition. Furthermore, their addition generally makes the compositions too thick for use as plastisol pastes.

Attempts have been made to use the conventional plasticizers to gain flexibility and then add other agents to improve the loss of other properties brought about by the use of such plasticizers. Attempts have been made, for example, to improve the strength and hardness by adding hardening agents with the plasticizers, but the results obtained heretofore have shown little promise. In many cases, the product formed after the curing of the hardening agent is a heterogeneous combination of two incompatible materials and it has very poor strength. Other of the suggested additives cannot be hardened during the short processing steps employed with the polymers and if the curing period is extended it has a deleterious effect on the polymer. The suggested hardening agents are also generally unsuited for use in the preparation of plastisols as they make the composition too thick for use as a spreadable paste.

It is therefore an object of the invention to provide a new class of plasticizers for the thermoplastic polymers. It is a further object to provide novel plasticizers for thermoplastic polymers which are relatively non-volatile and non-migratory. It is a further object to provide novel plasticizers for thermoplastic polymers that endow the resulting plasticized compositions with increased strength and toughness. It is a further object to provide plasticizers that endow thermoplastic polymers with excellent flexibility, even at the lower temperatures. It is a further object to provide novel plasticizers that may be readily polymerized in combination with the thermoplastic polymers to produce products which are very hard and tough but still highly flexible. It is a further object to provide novel liquid plasticizers which are ideally suited for use in preparing vinyl polymer plastisol and organosol compositions. It is still a further object to provide improved thermoplastic polymer compositions, and particularly vinyl polymer plastisol and organosol compositions. Other objects and advantages of the invention will be apparent from the following detailed description thereof.

It has now been discovered that these and other objects may be accomplished by employing as the plasticizing agent an ester of (1) a substituted 1,5-pentanediol wherein achain carbon atom immediately adjacent to one of the terminal hydroxy-bearing carbon atoms is a tertiary carbon atom, and a chain carbon atom adjacent to the other hydroxyl bearing carbon atom is a quaternary carbon atom, one of the carbon atoms to which the said quaternary carbon atom is attached being the carbon atom of an ether-substituted alkyl group, such as, for example, 2,4-dimethyl-2-methoxymethyl-1,5-pentanediool, and (2) carboxylic acids and/ or carboxylic acid esters and preferably I those acids and acid esters containing at least 6 carbon atoms. These particular esters have been unexpectedly found to be superior plasticizers for thermoplastic polymers, and particularly the vinyl halide polymers, as they are highly compatible therewith and when use, even in relatively small quantities, endow the said polymer compositions with many improved properties. Polymer compositions containing these esters have excellent flexibility, even at the lower temperatures, and improved strength and toughness. In addition, the compositions have been found to have excellent stability and can withstand long periods of use and exposure to air and high temperatures without loss of plasticizer through migration and/ or volatilization.

Corning under special consideration as plasticizer are the esters of the above-described substituted 1,5- pentanediols and unsaturated acids and/ or unsaturated acid esters, and preferably the acid esters of polycarboxylic acids, such as rnaleic acid, and ethylenically unsaturated monohydric alcohols, such as those of the allyl and vinyltype. It has been unexpectedly found that these particular esters, in addition to bestowing the above-described superior properties, may be cured in combination with thermoplastic polymers at a very rapid rate during the usual processing steps to produce homogeneous compositions wihch are extremely hard but still quite flexible. These preferred esters have been found to be particularly suited for use in preparing vinyl polymer plastisol and organosol compositions. When combined with the finelydividecl polymers, they form liquid mixtures that can be easily spread on cloth or metal panels and cured to produce very hard but flexible films. They are particularly suited for this and other applications as they are relatively non-volatile and the resulting plasticized compositions can be cured in an open system without fear of loss of plasticizerv The substitued 1,5-pentanediols used in producing the plasticizers of the invention comprise those polyols having a straight chain of five carbon atoms the terminal carbon atoms of which are joined to hydroxyl groups, a chain carbon atom adjacent to one of these terminal hydroxylbearing carbon atoms being a tertiary carbon atom, and the chain carbon atom adjacent to the other terminal hydroxyl-bearing carbon atom being a quaternary carbon atom which is joined to a carbon atom of an ether-substituted alkyl group. Examples of these polyols are 2,4-dimethyl-2-methoxymethyl-1,5 pentanediol, 2,4-dimethyl-2- hydroxyethoxymethyl-l,5 pentanediol, 2,4 di(methoxybutyl)-2-butoxymethyl-1,5:pentanediol, 2,4-diethyl-2 11ydroxyethoxymethyl-1,5-pentanediol, 2,4-di chlorobutyl Z-methoxymethyl-l,5-pentanediol, 2,4-dihexyl-2 butoxymethyl-1,5-pentanedio1, 2,4-dibutyl 2 ethoxyhexyloxymethyl-1,5-pentanediol, 2-butyl-.4 hexyl-2-propoxymethyl- 1,5-pentanediol, 2,4-(dicyanobutyl) 2 isobutoxymethyl- 1,5-pentanediol, 2,4-dicyclohexyl-2 allyloxymethyl 1,5- pentanediol, 2,4-didecyl-2-cyclohexoxymethyl-1,5 pentanediol, 2,4-diphenyl-2-methallyloxymethyl 1,5 pentanediol, 2,4-diisopropyl-Z-chloroethoxybutyl-1,5-pentanediol, 2,4-diphenyl-2 dodecyloxymethyl-1,5-pentanediol, 2,4-diethyl 2 diethoxybutoxymethyl 1,5 pentanediol, 2,4- di(chlorocyclohexyl)2-methallyloxybutyl 1,5 pentanediol, 2,4-dibenzyl-Z-phcnoxymethyl-1,S-pentanediol, and 2,4-dibromobutyl-2-cinnamyloxymethyl-1,5 pentanediol.

The preferred polyols are the substituted 1,5-pentanediols wherein the tertiary carbon atom joined to one of the terminal carbinol groups is joined to a carbon atom of a hydrocarbon radical or a substituted hydrocarbon radical as a haloor cyano-substituted radical wherein the said radicals contain from 1 to carbon atoms, and the quaternary carbon atom joined to the other terminal carbinol group is joined to a carbon atom of the same or different hydrocarbon or substituted hydrocarbon radical described above, and to an ether-substituted methyl group wherein the substituent attached to the methyl group is a member of the group consisting of OR radicals, OXOH radicals, OXOR radicals and i radicals, wherein R is a hydrocarbon radical, preferably containing from 1 to 18, carbon atoms and X is a polyvalent hydrocarbon radical containing from 1 to 7 carbon atoms. Examples of these preferred polyols are 2,4- dioctyl-Z-methoxybutoxymethyl-1,5-pentanediol, 2,4 didecyl-Z-ethoxymethyl-l,S-pentanediol,'2,4-diamyl-2 bcnzyloxymethyl-1,5-pentanediol, 2,4-diamyl 2 butoxyhexoxymethyl-1,5-pentanediol, 2,4-dioctyl-2 cyclohexyloxymethyl-1,5-pentanediol, 2,4-dicyclopentyl-Z-ethoxymethyl- 1,5-pentanediol, 2,4-diheptyl-2-trimethylheptyloxymethyl- 1,5-pentanediol, 2,4-diethyl2-valcroxybutoxymethyl 1,5- pentanediol, 2,4-dioctyl-2-(3',7'-diacetoxyheptoxymethyl) 1,5-pcntanediol, 2,4-dibenzyl-2 dodecyloxymethyl 1,5- pentanediol, 2,4-didecyl-2-ethoxymethyl-1,5 pentauediol, 2,4-diamyl2-acetoxybutoxymethyl-1,5 pentanediol, and 2,4-diamyl-2-hexyloxymethyll ,S-pcntanediol.

Particularly preferred polyols are those of the general formula:

wherein R is a hydrocarbon radical which is free of any type of aliphatic unsaturation, e. g. an alkyl, cycloalkyl, alkaryl, aryl, or arylalkyl radical, and preferably contains from 1 to 10 carbon atoms, and both Ris are identical alkyl radicals, preferably containing from 1 to 8 carbon atoms. Examples of these polyols are 2,4-dimethyl-2- methoxymethyl-1,5-pentanediol, 2,4-dibutyl 2 propoxymethyl-1,5-pentanediol, 2,4-dimethyl-2 isobutoxymethyl- 1,5-pentanediol, 2,4diamyl-Z-benzyloxymethyl-1,5 pentanediol, 2,4-diethyl-Z-hexyloxymethyl-1,5 pentanediol, 2,4dibutyl-2-butoxymethyl-1,5-pentanediol, 2,4-dimethyl- 2-n onyloxymethyl1,5-pentanedioi, 2,4-dihexyl 2 decyloxymethyl-1,5-pentanediol, 2,4-dioctyl-2 benzyloxymethyl-1,5-Pentanediol, and 2,4-diheptyl-2-cyclohexylmethoxymethyl-1,5-pentanediol.

Polyols of the above-described formula wherein R is an ether-substituted hydrocarbon radical XOR wherein R is a hydrocarbon radical, and preferably an aliphatic radical, containing from 1 to 10 carbon atoms and X is a bivalent aliphatic hydrocarbon radical, containing from 1 to 6 carbon atoms, come under special consideration, particularly because of the improved plasticizing properties of their esters. v

Polyols of the above-described formula wherein R is an XOH radical or an radical also come under special consideration as they may be reacted with the carboxylic acids or carboxylic acid esters to form products having at least three ester groups and improved plasticizing properties.

The above-described substituted l,5-pentanediols may be prepared by any suitable method. They may be prepared, for example, by reacting a 2,4-dihydrocarbyl-2- alkoxymethyl-1,5-dihalopentane with water, silver hydroxide or a strong base, or by hydrolyzing a substituted dihydropyran and hydrogenating the resultant product. The polyols may also be prepared by hydrogenating the corresponding substituted 1,5-pentanediols, or the lactones prepared from these 1,5-pentanediols.

The acids used in preparing the ester plasticizers may be monocarboxylic or polycarboxylic, saturated or unsaturated, and may be aliphatic, alicyclic, heterocyclic or aromatic. They may also be substituted if desired with. substituents, such as halogen atoms, alkoxy radicals, and the like. Illustrative examples of these acids are acetic acid, butyric acid, hexanoic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, hendecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidicacid, angelic acid, sorbic acid, hydrosorbic acid, 2-oc-tenedioic acid, acrylic acid, methacrylic acid, crotonic acid, alpha-chloroacrylic acid, 2,8-decadienoic acid, 2,5- heptadienoic acid', cyclohexanoic acid, cyclopentenoic acid, butylcyclohexanoic acid, tartaric acid, benzoic acid, naphthoi c acid, toluicac'id, 'methylbenzoic acid,-.nonylbenzoic acid, nicotinic acid, succinic acid, glutaric acid, diglycolic acid, pimelic acid, ketopimelic .acid, suberic acid, azelaic acid, brassylic acid, maleic acid, fumaric acid, glutaconic acid, hydromuconic acid, 3-hexene-1,2;3,4-tetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimesic acid, pyromellitic acid, l,4-cyclohexanedicarboxylic acid, 'cyclohexaneacetic acid, chlorocyclohexanoic acid, dibromotoluic acid, and citric acid. Preferred acids of this group comprise the monocarboxylic acids containing from 1 to-18 carbon atoms and the dicarboxylic acids containing from 2 to 16 carbon atoms.

Particularly preferredacids to be used in'preparing the ester plasticizers comprise the monocarboxylic acids containing at least 6 carbon atoms and preferably the aliphatic acids containing from 6 to 18 carbon atoms and the aromatic monocarboxylic acids containing from 7 to 14 carbon atoms and having the carboxyl group attached directly to the aromatic ring, such as caprylic, caproic, 2-ethylhexanoic, 3,5,5-tn'methylhexanoic, pelargonic, capric, lauric, myristic, palmitic, benzoic, toluic, methylbenzoic, isopropylbenzoic, tert-butylbenzoic, and the like. Special members of this group comprise the alkanoic acids containing from 6 to 15 carbon atoms and the aryl monocarboxylic acids containing from 7 to 12 carbon atoms.

Coming under special consideration, particularly because'of the use of their esters as polymerizable plasticizers for the vinyl polymers, are the unsaturated aliphatic monocarboxylic acids containing from 3 to 15 carbon atoms, such as acrylic acid, methacrylic acid, hexadienoic acid, andthe like. Special members include the alkenoic acids containing from 3 to carbon atoms.

Acid esters may also be used to prepare the ester plasticizers. The acid esters employed for this purpose are those obtained by esterifying at least one and at most all but one of the carboxyl groups of a polycarboxylic acid 'with a monohydric alcohol. The polycarboxylic acids used for this purpose may be any of those described above for the direct esterification of the substituted 1,5- pentanediols. The monohydric alcohols may be aliphatic, aromatic or heterocyclic, saturated or unsaturated, such as methanol, ethanol, butanol, cyclohexanol, allyl alcohol, methallyl alcohol, benzyl alcohol, cyclopentenol, furfuryl alcohol, tetrahydropyran 7 2 methanol, dihydrofuran-Z- ethanol, Z-methylcyclohexanol, and the like. Preferred alcohols of this group comprise the aliphatic monohydric alcohols containing from 1 to 8 carbon atoms and the heterocyclic alcohols containing from 4 to carbon atoms and having at least one oxygen, sulfur or nitrogen. Particularly preferred atom in the cyclic structure. monohydric alcohols are the unsaturated alcohols of the allyl and vinyl-types, i. e., the alpha,beta-ethylenically unsaturated alcohols and beta,gamm'a-ethylenically unsaturated alcohols, suchas vinyl alcohol, l-propen-l-ol, l-hexen-l-ol, 3-chloro-1-buten-l-.ol, allyl alcohol, crotyl alcohol, cinnamyl alcohol, 2,4-hexadien-laol, 3-chloro-2- buten-l-ol, and the like. Especially preferred as the 2- alkenols containing from 3 to 10 carbon atoms and the l-alkenols containing from 2 to 8 carbon atoms.

Special acid esters to be used in preparing the novel esters are the esters of the polycarbocyclic acids containing from 2 to 16 carbon'atoms and the aliphatic monohydric alcohols containing from 1 to 8 carbon atoms.

Particularly preferred because of the value of the result ing esters as polymerizable plasticizers for the plastisol and organosol compositions are .the acid esters of the un-;

saturated dicarboxylic acids containing from4 to 12 carbon atoms and the above-described allyl and vinyl-type alcohols.

ate, 2,4-dihexyl-2-butoxymethyl-1,5-pentanediol dipelar gonate, 2,4 diisopropyl-2-chloroethoxybutyl-1,5-pentanediol dilaurate, 2,4-diphenyl-2-dodecyloxymethyl-1,5-penmethyl-1,5-pentanediol diacrylate, 2,4-dimethyl-2-meth- The ester plasticizers are obtained by esterifyingthe' above-described substituted 1,5-pentanediols with one or moreof the above-described carboxylicacids and/ or acid esters. Illustrative examples of the 'novel estersinclude 2,4 dimethyl-Z-methoxymethyl-1,5-pentanediol dicapryloxymethyl-1,5-pentanediol acrylate laurate, 2,4-dichlorobutyl-2-isobutyoxymethyl-1,5-pentanediol vbis(allyl maleate), 2,4 dimethyl-Z-methoxymethyl-1,5-pentanediol bis (vinyl succinate), the polyester of 2,4-dibutyl-2-allyloxy methyl 1,5 -pentanediol succinate, the polyester of 2,4- dichlorocyclohexyl-Z-methoxymethyl-1,S-pentanediol and phthalic acid, and the polyester of 2,4-dimethyl-2-dodecyloxymethyl-1,5-pentanediol and 1,2,4-butanetricarboxylic acid.

Preferred esters are those obtained by reacting the sub-- stituted pentanediols with the above-described preferred monocarboxylic acids containing at least 6 carbon atoms and the above-described preferred acid esters of the polycarboxylic acids and the aliphatic monohydric alcohols containing from 1 to 10 carbon atoms, such as 2,4-dimethyl-Z-methoxymethyl-1,5-pentanediol dicaprylate, 2,4- dibutyl-2-methoxymethyl-1,5-pentanediol allyl maleate vinyl succinate, 2,4-dihexyl-Z-ethoxymethyl-1,5-pentanediol bis(al1yl adipate), and 2,4-dimethyl-2-ethoxymethy1-1,5- pentanediol dibenzoate.

Of particular interest are the esters of the preferred substituted pentanediols and the above-described unsaturated monocarboxylic acids and the acid esters of the unsaturated dicarboxylic acids and the allyl and vinyl type alcohols.

The preferred neutral esters prepared from the alcohols of the above described formula wherein R is an -XOH or an 0 XOgR radical may be exemplified by 2,4-dimethyl-2-butanoyloxyethoxymethyl 1,5 pentanediol dibenzoate, 2,4 di methyl 2-hexanoyloxyethoxymethyl-1,5 pentanediol dicaprylate, 2,4 diethyl-2-octanoyloxyethoxymethyl 1,5- pentanediol, and the like.

The above-described esters may be prepared by any suitable method. They are preferably prepared by direct esterification wherein the substituted 1,5-pentanediols are reacted with the desired carboxylic acid or the carboxylic acid ester.. According to this method, the acids (or their anhydrides). and/ or the acid esters are combined with the substituted 1,5-pentanediols and the resulting mixture heated together, the water formed during the reaction being removed, preferably by distillation. Esterification The amount of the acid component and substituted 1,5- I

pentanediol to be used in the reaction will vary depending upon the product and the process selected. In general,

the acid component is reacted with at least a chemical equivalent amount of the polyol. As used throughout the specification and claims, the expression chemical equivalent amount refers to that quantityrequired to furnish approximately one carboxyl group for every hydroxyl group of the alcohol molecule. Preferably, the alcohol and acid are reacted in chemical equivalent ra tios varying from lzlto 1:5, respectively.

The esterification may be accomplished in the presence or absence of solvents or diluents. In case solvents or dilnents are desired, organic compounds, such as benzene, toluene, cyclohexane, xylene, and mixtures thereof, which do not interfere with the reaction may be'utilized.

The temperature employed in the esterification process may vary over a considerable range. In general, temperatures varying between about 70 C. and 150 C. are preferred. Particularly preferred temperatures range from 80 C. to 100 C.' Higher or lower temperatures may be utilized, however, if desired or necessary. Atmospheric, superatmospheric, or subatmospheric pressure may be employed.

The separation of the esters formed in the may be accomplished by any suitable means, extraction, distillation, fractional precipitation,

u The polymers tobe plasticized with the above-described esters may be any thermoplastic polymer and preferably a thermoplastic polymer of a monomer containing a group. The term polymer is employed throughout the specification and claims in a generic sense to refer to the homopolymers, copolymers and interpolyrners of these particular monomers. Examples of these monomers include the alkenyl-substituted aromatic compounds as styrene, alphamethylstyrene, dichlorostyrene and vinyl naphthalene; the alkyl esters of the mono-and polycarboxylic unsattu'ated acids as methyl acrylate, methyl methacrylate, butyl methacrylate and, propyl acrylate, dimethy-l maleate, dibutyl fumarate and dihexyl maleate; the alkenyl esters of the saturated monocarboxylic acids as allyl acetate, methallyl butyrate, vinyl benzoate, vinyl valerate and vinyl caproate; the vinylidene halides as vinylidene chloride and vinylidene fluoride; the vinyl halides as vinyl chloride and vinyl bromide; the unsaturated nitriles as acrylonitrile and methacrylonitrile; the unsaturated ethers as vinyl ethyl ether, vinyl butyl ether, and allyl octyl ether; and the unsaturated ketones, such as vinyl butyl ketone, vinyl ethyl ketone, and the like.

A preferred group of polymers to be plasticized are the vinyl halide polymers. Particularly preferred are the vinyl halide polymers containing a predominant quantity, i. e., at least 60%, of the monomeric units as vinyl halide units as vinyl chloride, vinyl bromide, vinyl iodide or vinyl fluoride. Particularly preferred polymers are the vinyl chloride polymers having 90% to 100% vinyl chloride units.

The polymers employed may have a variety of molecular Weights. The preferred polymers, and this is particularly true when they are to be used in the preparation of plastisols and organosols, are those having a molecular Weight as measured by the Staudinger method described in Ind. Eng. Chem. vol. 36, p. 1152 (1936), of at least 15,000, and preferably above 20,000. Commercial grades of vinyl chloride polymers having molecular weights between 100,000 and 200,000 are particularly suited for use with the above-described polymerizable plasticizers.

If the polymers are to be used in the preparation of plastisol and organosol compositions they should preferably be in a finely-divided state of subdivision. Generally, they should have a size of less than five microns and more particularly a size between 0.1 and 1 micron.

The plasticizers of the present invention may be added tothe polymers singly, in admixture or in combination with other plasticizing materials. The addition of other types of plasticizing agents along with the plasticizers of the present invention is desirable in many cases and particularly in those instances where the composition is to be a plastisol or organosol. Examples of these secondary agents include the phosphoric acid esters of phenols or aliphatic alcohols such as tricresyl phosphate, the alkyl and alkoxyalkyl esters of dicarboxylic acids and particularly the alkyl and alkoxyalkyl esters of the aromatic acids, such as dibutyl phthalate, diamyl phthalate and di'oct-yl phthalate.

The amount of the plasticizer to be added to the thermoplastic polymer will vary over awide range depending on the type of product desired. If the polyreaction such as and the mers are to be used to produce calendered sheets or rigid molded articles, the amount of the plasticizer generally.

will vary from 30 parts to ISO-parts per 100 parts of polymer. Preferred amounts vary from 40 to parts per parts of polymer. If other types of plasticizing agents are employed, these proportions may be reduced considerably. Generally the amount of the novel plasticizers will vary from 20 to 70 parts and the secondary plasticizer from 50 to 20 parts.

If the polymers are to be used in preparing plastisols, the amount of the plasticizer employed will depend upon that required to form a fluid spreadable paste with the polymer at normal temperatures (e. g. about 20 C.). The resulting composition preferably should have a viscosity not greater than 1000 poises at 20 C. and preferably between 50 and 400. Generally the desired results are obtained by employing from 40 parts to parts of the liquid plasticizer. All but about 20 parts of this could be replaced by other plasticizers.

In the case of organosols, the liquid vehicle will contain added solvents, such as xylene, and increased amounts of plasticiser may be tolerated. Preferred amounts of plasticizer in these cases vary from 60 parts to 110 parts per 100 parts of polymer. The amount of solvent employed generally varies between 1 to- 20 parts and in some cases as high as 30 parts per 100 parts of polymer.

If the ester plasticizers are unsaturated, catalysts may be added to the composition to accelerate the polymerization of the said esters in combination with the polymers. Preferred catalysts are the peroxide catalyst, such as benzoyl peroxide, tertiary butyl perbenzoate, ditertiary butyl diperphthalate, tertiary butyl peracetate, and the like, and mixtures thereof. Particularly preferred catalysts are the di-tert-alkyl peroxides. The amount of the catalyst added will generally vary from 0.01% to 5% and more preferably from .1% to 2% by weight of the polymer.

Various pigments, colors, fillers and resin stabilizers may be added to the compositions. Many of the resins, such as the vinyl halide polymers, may undergo a slight discoloration when subjected to the high temperatures employed in the curing process so it is advisable toadd materials known tostabilize the polymers against discoloration by heat.

The polymers and plasticizer may be compounded together by means of any of the conventional equipment, such as mills of the heated roll type or internal mixers. The plasticizer and other compounding, ingredients are worked into the polymer so that they are thoroughly dispersed therein, and the resulting composition then molded, calcndered, extruded or otherwise formed into the desired articles.

In the case of the polymerizable plasticizers, the temperatures employed during the milling and molding and subsequent treatment should be suflicient to bring about the desired degree of polymerization of the esters. In the presence of the aforedescribed active catalysts, the polymerization may be accomplished at a relatively rapid rate at temperatures between 100 C. and 200 C. and preferably between C. and 200 C. The esters may be completely polymerized in the presence of the polymers or the polymerization may be carried only to partial completion in order to produce products having various degrees of hardness.

To illustrate the manner in which the invention may be carried out the following examples are given. It is to be understood that the examples are for the purpose of illustration and the invention is not to be regarded as limited to any of the specific compounds or conditions recited therein. Unless otherwise specified, parts disclosed in the following examples are parts by weight.

Example I About 88- parts of 2,4-dimethyl-Z-rnethoxymethyl-1,5-

pentanediol was mixed with 125 parts of benzene, 283

parts; of capric acid, and 1.25 parts of p-toluenesulfonic acid and the resulting mixture heated under reflux for several hours while fthe theoretical amount of. water was collected as an azeotrope. Distillation of the resulting mixture yielded 134 parts of 2,4-dimethyl-2-methoxymethyl-1,5-pentanediol dicaprate, a viscous liquid having the following properties: B. P. 195-197 C. (0.04 mm); n 20/d1.4520; Sp. Gr. 20/4 0.9286. Analysis.-'C% found 71.65, calc. 71.85; H% found 11.54, calc. 11.64; ester value 0.413 eq./100 g., calc. 0.453 eq./100 g.; hydroxyl value 0.003 eq./ 100 g.

100 parts. of polyvinyl chloride was combined with 60 parts of the 2,4-dimethyl-2-methoxymethyl-1,S- entanediol dicaprate by mixing the two ingredients together with two parts (per 100 parts polymer), of a trade stabilizer, milling the mixture together on a roll mill at a temperature between 130 C. and 150 C. and then molding the resulting sheet at 160 C. for'two minutes. Some of the properties of the resulting sheet are shown in the following table in comparison to a similar sheet plasticized with Example [I 100 parts of polyvinyl chloride was combined with 50 parts of 2,4-dimethyl-2-ethoxymethyl-1,5-pentanediol dibenzoate by mixing the two ingredients together with two parts (per 100 parts of polymer) of a trade stabilizer, milling the mixture together on a roll mill at a temperature between 130 C. and 150 C. and then molding at 160 C. for two minutes. The resulting plasticized sheet possessed good tensile strength, flexibility over a wide range of conditions, low volatility loss and excellent color and heat stability.

Example 111 A plastisol composition is prepared by combining 100 parts of finely-divided poly(vinyl chloride) with 60 parts of 2,4-dimethyl-2-ethoxymethyl-1,5-pentanediol dicaproate, 10 parts of di(2-ethylhcxyl)phthalate, and 3 parts of a polyvinyl chloride stabilizer and the resulting mixture mixed together to form a spreadable fluid paste. The paste is then spread on metal panels at a thickness of 8 mils (0.008") with a doctor blade and the films baked at 177 C. for minutes. At the completion of the baking period, the films are clear homogeneous compositions which have excellent flexibility.

Example IV A plasticized composition is prepared by mixing 50 parts of a polyester of 2,4-dimethyl-2-methoxymethyl- 1,5-pentanediol and phthalic anhydride (obtained by reacting 88 parts of the alcohol with 90 parts of the anhydride) with 100 parts of poly(vinyl chloride) and 2 parts of a trade stabilizer, milling the mixture together at a temperature between 130 C. and 150 C. and molding the resulting sheet at 160 C. for two minutes. The resulting sheet possesses good tensile strength and excellent flexibility even at temperatures below about 0 C. In addition, the sheet has approximately zero volatility loss and has a very low water extraction value.

Example V An organosol composition is prepared by mixing 100 parts of finely-divided poly(vinyl chloride) with 40 parts 2,4-dimethyl-2-ethoxymethyl-1,5 pentanediol diacrylate, 20 parts of dioctyl phthalate, 3 parts of a polyvinyl chloride resin stabilizer, 3 parts of dietertiary butyl diperph- I thalate and parts of a solvent comprising toluene and high boiling naphthalenes and mixing the ingredients together to form 'a spreadable mixture. This mixture is spread on metal panels and baked at 177 C. The re-' sulting films are homogeneous compositions and are very hard and tough but quite flexible. 7

Films having related properties may be obtained by toplacing the diacrylate esters in the above-described proc- I ess with equivalent amounts of each of the following esters: 2,4-dimethyl-Z-butoxymethyl-1,5-pentanediol dimethacrylate, 2,4-dibutyl-2 allyloxy-methyl-1,5-pentanediol di-Z-butenoate, and 2,4-dihexyl-2-butoxymethyb1,5- pentanediol di2,4-hexadienoate.

Example VI parts of finely-divided poly(vinyl chloride) with 60 parts of 2,4 dimethyl 2-ethoxymethyl-1,S-pentanediol bis(ally1 maleate), 20 parts of di-octyl phthalate, 3 parts of polyvinyl chloride stabilizer and 2 partsof tertiary gether to form a spreadable paste.

butyl perbenzoate, and the resulting mixture mixed to- The paste is then spread on metal panels. at a thickness of8 mils'with a doctor blade and the films baked at 177 C. for 5 minutes. At the completion of the baking period, the films are homogeneous compositions which are very tough and hard with a leathery feeling-but still quite flexible.

Films having related properties may be obtained by re- 7 placing 2,4-dimethyl-2-ethoxymethyl-1,5-pentanediol bis- (allyl maleate) in the above process with equivalent amounts of each of the following esters: 2,4-dimethyl-2- methoxymethyl-l,5-pentanediol bis(vinylmaleate), 2,4- dimethyl-Z-butoxymethyl-l,S-pentanediol bis(methallylfumarate), 2,4-dimethyl-2-hexoxymethyl-1,5-pentanediol bis(al1ylglutaconate) and 2,4-dimethyl 2rethoxymethyl- 1,5 -pentanediol bis(furfuryl maleate).

Example VII '40 parts of a triester of valeric acid and 2,4-dimethyl- Z-hydroxyethoxymethyl-l,S-pentanediol (obtained by reacting 1 mole of the alcohol with 3 moles of the valeric acid) is combined with parts of a copolymer of 90 parts vinyl chloride and 10 parts vinylidene chloride, two parts of a trade stabilizer, and the mixture milled together on a roll mill at a temperature between C. and C. and then molded at C. for two minutes. The resulting plasticized sheet possesses good flexibility, low volatility loss and good color and heat stability.

Plasticized compositions having related properties are obtained by replacing the valeric acid ester in the above process with equivalent amounts of each of the follow ing esters: triester of caproic acid and 2,4-dibutyl-2-hydroxyethoxymethyl-1,5-pentanediol, triester of caprylic acid and 2,4-dimethyl-2-hydroxyethoxymethyl-1,5-pentanediol and the triester of 2-e thylhexanoic acid and 2,4- diethyl-2-hydroxyethoxymethyl-1,S-pentanediol.

I claim as my invention: 1. A composition comprising a thermoplastic polymer of a monomer containing a single ethylenic group and a plasticizing amount of an ester of (1) a substituted 1,5-pentanediol wherein the chain carbon atom immediately adjacent to one of the terminal hydroxyl bearing carbon atoms is joined to an alkyl side chain containing up to 8 carbon atoms and the chain carbon atom adjacent to the other hydroxyl carbon atom is joined through one valence bond to an alkyl side-chain containing up to 8 carbon atoms and through another valence bond to a member of the group consisting of -CH2OR, -CH2OXOH, --CH2OXOR and radicals wherein R is a hydrocarbon radical containing from 1 to 18 carbon atoms and X is a divalent hydrocarbon radical containing from 1 to .7 carbon atoms and (2) an acid component of the group consisting of monocarboxylic acids containing up to 18 carbon atoms, dicarboxylic acids containing from 2 to 16 carbon atoms and acid esters of the aforementioned dicarboxylic acids and monohydric alcohols containing up to 8 carbon atoms.

2. A composition as defined in claim 1 wherein the substituted 1,5-pentanediol is a 2,4-dialkyl-2-alkoxymethyl- 1,5-pentanediol wherein the alkyl radical contains up to 8 carbon atoms and the alkoxy radical contains up to 10 carbon atoms.'

3. A composition comprising a thermoplastic polymer of a monomer containing a single CH2=C= "roup and from 20 parts to 100 parts per 100 parts of polymer of a plasticizer comprising an ester of a 2,4-dialkyl-2-alkoxymethyl-1,5-pentanediol wherein the alkyl radical contains up to-8 carbon atoms and the alkoxy radical contains up to 10 carbon atoms and (2) a hydrocarbon monocarboxylic acid containing from 6 to 18 carbon atoms.

4. A plastisol composition comprising a spreadable fluid mixture of a finely-divided vinyl chloride polymer containing at .least 90% vinyl chloride units therein and having a molecular weight above 20,000 dispersed in a liquid vehicle containing about 20% to 70% by weight of the said polymer of an ester of (1) a substituted 1,5- pentanediol wherein a chain carbon atom immediately adjacent to one of the terminal hydroxyl-bearing carbon atoms is joined to an alkyl side chain containing from 1 to 8 carbon atoms, and the chain carbon atom adjacent to the other hydroxyl-bearing carbon atom isjoined to an alkyl radical containing from 1 to 8 carbon atoms and to an ROCI-Izradical wherein R is an aliphatic hydrocarbon radical containing from 1 to 10 carbon atoms, and (2)- an acid ester of an aliphatic unsaturated dicarboxylic acid containing upto 16 carbon atoms and an ethylenically unsaturated monohydric alcohol consisting up to 8 carbon atoms, and 0.01% to 5% by weight of a peroxide polymerization catalyst.

5. A hard, tough, flexible composition obtained by subjecting the composition in claim 4 to a temperature between 100" C. and 200 C. t

6. A composition as defined in claim 4 wherein the ester is 2,4-dimethyl-2-ethoxymethyl1,5-pentanediol bis- (allylmaleate) 7. A plasticized composition comprising a thermoplastic vinyl halide polymer and from 20 parts to 100 parts per. 100 paits of polymer of an ester of a 2,4-dialkyl-2-alkoxymethyl-1,5-pentanediol wherein the alkyl radical contains up to 8 carbon atoms and the alkoxy radical contains up to 10 carbon atoms and a monocarboxylic acid containing no more than 18 carbon atoms.

8. A composition as defined in claim 7 wherein the ester is 2,4-dimethyl-Z-methoxymethyl-l,S-pentanediol dicaprate.

9. A composition as defined in claim 7 wherein the ester is 2,4-di-methyl-2-ethoxymethy1-1,5-pentanediol dizbenzoate.

10. A composition as defined in claim 7 wherein the ester is 2,4-dimethy1-2-ethoxymethyl-l,S-pentanediol diacrylate.

11. A composition comprising vinyl chloride polymer and a plasticizer consisting of a triester of an alkanoic acid containing up to 10 carbon atoms and a 2,4-dialkyl- 2-hydroxyalkoxymethyl-1,5-pentanediol.

No references cited. 

1. A COMPOSITION COMPRISING A THERMOPLASTIC POLYMER OF A MONOMER CONTAINING A SINGLE ETHYLENIC 